Method of esterification



Sept.` 18, 1945. J. H. BRUUN ErAL I METHOD 0F ESTERIFICATION Filed Aug. 7, 1942 @Hmm MW mm QV EN QU ww i M gw nf n @i www HW Patented Sept. 18, 1945 UNITED STATES PATENT ori-'ICE METHOD F ESTERIFICATION Johannes H. Brunn, Swarthmore, and .John Harold Perrine, Prospect Park, Pa., asslgnors to Sun Oil Company, Philadelphia, Pa., a corporation of New Jersey v Application August 7, 1942, Serial No. 454,042

2 Claims. (Cl. 26o- 410) The present invention relates to a method o! producing esters and is particularly concerned with a method of producing esters by reacting a relatively high molecular weight acid with a relatively high molecular weight alcohol under such conditions that the acid and alcohol being reacted, as well as the esters produced, remain in liquid phase during the`esteriflcation reaction. The invention is particularly directed to a novel continuous catalytic method of producing esters of the above type in such a manner that a much higher than ordinary equilibrium is reached in a very short time, giving a high yield of goed quality ester. A

For better understanding of the present invention, reference' should be made to the accom panying drawing, the single gllre oi which is a flow chart of an apparatus suitable for practicing the present invention.

In the' drawing, I designates a storage tank for organic acids to be esterified, t represents a storage tank for the alcohol to be esteried, while 3 represents a storage tank for the catalyst to the mixed reactants and catalyst new through.

line il to heater I2 wherein they are heated to the desired reaction temperature by heat ex= change with suitable heating medium. If necessary, a trap i3 may be provided in line il between mixer it and heater i2 in order to remove from the mixed reactants any sludge formed on mixing. From heater l2, the mixed reactants flow through valved line Ill to the top tray of bubble cap column I5.

The bubble cap column i5 is of conventional design and the mixed reactants now downwardly therethrough in liquid phase in thel usual manner, a pool of liquid being maintained on each tray I6 and the liquid overflowing through downcomer il to the next lower tray and so through the column. Vapors rise through the column through vapor risers I8 and are forced to bubble through the pool of liquid on each tray by double caps I9.

The reactants and catalyst in bubble cap column I5 are maintained at the desired reaction a substantial amount of esters.

temperature and during theirdownward course through the column, the alcohols and acids react to form esters, so that the liquid overflowing from the bottommost tray in the column contains The esteriiied product is withdrawn from bubble tower Il through trapped line 20 by pump 2i and passes to suitable storage, or purification means, as hereinafter are more fully described.

An inert entrainer gas, withdrawn from storage tank 22 through valved line 23, is admitted into the lowermost portion of the bubble cap column I '5 and rises therethrough in vapor phase in the usual manner. Under the conditions employed in the bubble cap column i5, the water formed by the esterification reaction will be vaporized and will pass out the top of the column along with the entrainer gas. The mixed entrainer gas and water vapors are removed from the bubble cap column I5 through valved line 24 and pass to condenser 2B wherein the Water is condensed. Thence, the mixed Water and gas flow to surge tank 2B, the water being withdrawn from the bottom thereof through line 21 having a float controlled valve 4,8 therein. The

entrainer gas is withdrawn from the top of tank 26 through line 285, is recompressed by compressor 29 and ows through valved line 3D back to storage tank 22 for reuse.

The es teried product withdrawn from the bottom of bubble cap column I5 through trapped line at by pump ZI may flow through valved line tI to suitable purification means. Such purincation means are here illustrated as a wash tank t2, the mixed esters, with any unreacted alcohols and acids contained therein, being introduced at a point near the bottom of tank 32 while the aqueous solution of a suitable alkali, an alkali metal or an alkaline earth metal, hydroxides or their equivalent, is introduced at a point near the top of tank 32 through valved line 33. In wash tank 32 lany unreacted acids are converted into their corresponding soaps and are washed from the rising stream oi esters and unreacted alcohols, the soap solution being withdrawn from the tank 32 through valved line J4 and removed from the system, although, of course, it is to be understood that the acids may subsequently be recovered and recirculated. The mixed esters and alcohols free of unreaeted acids are removed from the top of wash tank 32' through valved line 35 and may then now through suitable apparatus for separating the esters from the alcohol. Suitable separation equipment is here illustrated as a stilllB in which the alcohol and esters are heated and vaporized. The vapors pass to tractionating column 38, the lower boiling constituent being withdrawn therefrom as an overhead vapor fraction through line 3l while the higher boiling constituent condensed therein is withdrawntherefrom through line $9.

Assuming that the alcohol is lower boiling than the ester produced, it will be the alcohol which is removed overhead through line 3l and it may pass therethrough to condenser so wherein it is cooled and condensed and through which it flows to surge tank di from which the alcohol is removed through line d2 having doet controlled valve 43 therein and thence it may ow through valved line M back to alcohol storage tank 2 for recirculation through the system.

The esters removed from vaporizer 88 through line :it by pump @a may be pumped to storage tank 65.

The foregoing is a brief outline of the now of reactants through our process. There are a'num ber of variable factors in the process and the exact conditions of reaction are a function of the inter-relation of the numerous variable factors eflecting the reaction. The principal variables in the 'process are the type and quantity of the acids being esteried, they type and quantity oi alcohol employed, the type and ntity oi catalyst employed, the temperature of reaction, the time of reaction and the pressure of reaction. The yield obtained, both qualitatively and quan titatively, is, as stated, a function of the interrelation of all these variable factors. With a given acid, alcohol and catalyst, we have found that the temperature and time of the reaction, exert the greatest influence. The present invention is adapted to be carried out at low pressure, atmospheric or slightly above or below atmospheric,

and reasonable variations in pressure do not' greatly aect the yield of esters. The time of reaction has amarked eiiect on the yield and it is necessary to permit a sucient time of reaction for the desired degree oi esteriiication to take place under the other conditions employed.' Lilre most processes, the temperature has a marked eiect on the yield and also on the time required for the desired equilibrium to be reached. 'We have found that within the range where esterication will proceed, an increase in temperature oi about 10 C. approximately doubles the rate of reaction. Too high a temperature should not be employed since excessive temperatures will result in discoloration of the product and deposition of charred matter in the reaction zone.

We have found that the temperature ot reaction should -be at least 100 C. in order that the relatively high equilibrium may be reached in a reasonable length of time. However, the temperature should not be much over 150 C. or certain of the products will be discolored. As a practical matter, we believe that a temperature of about 135 C. is best suited to give a high yield of good quality esters in a reasonable period of time. At thistemperature, 135 C., about 20 minutes reaction time is required in order to produce a. product having an acid number less than 4. Since a product with this acid number is suitable for many commercial uses, we prefer to directly, in accordance with our process, produce a product of this quality and, therefore, preferably provide a reaction time suiiicient for a product oi such quality to be produced. However, it should be understood that a product (ester) of lower quality, i. e., one having a higher acid number, may

caseros be produced by shortening the time of reaction or lowering the temperature of reaction and the product may then subsequently be further purined, for instance, by washing with an alkali to remove the unreacted acid, as hereinbefore described.

The present process is particularly adapted to esterifying acids having a boiling point above the temperature employed i'or the reaction. The acids, which we prefer to employ, are acids having physical properties similar to the usual fatty acids. Any of the ordinary iatty acids may be employed, oleic, stearidpalmitic, and the like; or acids derived from petroleum, either those naturally present therein, generally called naphthenic acids, or those obtained by partial oxidation oi selected fractions of petroleum.

A great many catalysts are suitable for use in the present process. The catalyst commonly used in corrunercial esterlcation processes is sulfuric acid but numerous other catalysts have been prod and may be employed. Suitable examples of such other catalysts are hydrochloric acid, or other strong mineral acids. However, it must be borne in mind that am strong acid may cause decomposition of a, tertiary alcohol. Phosphoric acids are less destructive and may be employed. The sulfonic acids, particularly those containing several carbon atoms, are desirable catalysts on account of their high eiiiciency, solubility and lees destructive action. Acid salts, such as mennendium sulfate and salts of any strong acids with Weak bases,` such as aluminum sulfate, may be employed. Zinc chloride has been found to be superior to other chlorides when used along with hydrochloric or sulphuric acid. Metallic scan", such as aluminum stearato or llnoleate, lead cleats and magnesium oleate, are useful catalysts. 1i the catalyst employed is a solid or liquid, under the reaction conditions in bubble cap column t5, it is mined with the reactants andintroduced into the top of the column as described. However, if the catalyst is such that it is a vapor, under the conditions employed in bubble cap column l, ier instance gaseous hydrochloric acid, the valve in line il@ is closed and the valve in line il is opened so that the gaseous catalyst is introduced into the :bottom of bubble cap column iii along with the entrainer gas owing through valved line 23. The gaseous catalyst then passes up through the column in vapor phase and is intimately med with the reactants therein.

The amount of catalyst, which it is necessary to add to the reactants, is relatively small. We have found that no substantial improvement in the yield is obtained when the amount of catalyst employed exceeds 5 percent by weight ci the acids being esterifled. We have obtained very satisfactory yields using approximately 3.2 per cent or less of sulphuric acid as a catalyst by weight of the acids being esteriiled.

The exact proportion of reactants which must be employed is subject to considerable variation However, one of the advantages of our process is that a high yield of good quality ester may be obtained when using a relatively small amount of alcohol. We have found that there is no substantial improvement in the yield of esters, either qualitatively or quantitatively, when the ratio of alcohol to acids is increased above 2 to l. A somewhat lower ratio may be employed by maising a slight sacrifice in the quantity of the esters produced.

When the acids to be esteriiied are those den rived from petroleum, there is frequently present therein acidimpurities which are readily attacked by, or react with, sulphuric acid on mixing to form sludge-like products. We, therefore, provide the trap I3 in line l I in order to remove such sludgelike products before the mixture is introduced into bubble cap column I5, the sludge being'removed from trap I3 through valved line 50 constantly or intermittently as desired.

ln order to better describe the present invene tion, the following example is given.

Puriiied naphthenic acids, obtained by partial oxidation of a naphthenic type kerosene and which -had an average molecular weight of 225 and an acid number of 220, were employed. The alcohol employed was commercial lauryl alcohol. These acids and alcohol were mixed, a molar ratio of alcohol to-acids of 2 to 1 employed, and 3.2

per cent sulphuric acid was mixed with the reactants to serve as a catalyst. During mixing the reactants were heated to 60 C. A small amount of sludge was formed during the mixing and was removed. The mixed reactants and catalyst were then heated to 135 C. and introduced into the top of a 40 plate bubble cap column at such a rate .that minutes were required for the reactants to pass through the column. 'I'he column was maintained at atmospheric pressure and was heated by a suitable heating jacket and a temperature of 135 C. was maintained through- -out the column. Butane, heated to 135 C., was

introduce'd into the bottom of the' column and was used as the entrainer gas, approximately equal molar parts of butane and ac ids being employed. The esterifled product Withdrawn from the bottom of the bubble cap column was distilled in order to remove the unreacted alcohol which was recirculated. The crude esters remaining after the distillation had an acid number of 6.9, showing that a yield oi. 96.9 per cent of the theoretical, based on the amount of acids charged to the process, was obtained. The crude esters had a boiling point ,ofA 145270 C. at 1 mm. These acids were then. purified by washing with sodium carbonate solution whereby most of the unreacted acids were saponiiiedand removed. The esters were then dried and a yield of puried esters equal to 95 per cent of the crude esters was obtained., These esters had a boiling point of l245 C. at 0.25 mm. and an acid number of 1.4.

We claim:

l. In the method of producing esters by reacting an alcohol with an organic acid, each of said reactants having a boiling point higher than the temperature used in the esterification reaction, the improvement which comprises forming a mixture of the acid and the alcohol, ilowing a stream of the mixture downwardly through a reaction .zone maintained at a temperature of 1D0-150 C.

and countercurrent to a stream of inert gas, intimately commingling said mixture with said inert gas Within said reaction zone in the presence of an esteriiication catalyst whereby the inert gas iirst comes in contact with a mixture containing a predominant proportion of esters and lastly comes in contact with the unesteried mixture of acids and alcohol, maintaining said reactants within said zone for a.relatively short time but sutiicient to obtain a high degree of esteriiication, withdrawing the esteried product from said zone at a locus near the locus of introduction of the inert gas and withdrawing the inert gas and water produced in the esterication reaction from said zone at a locus near the locus of introduction of the reactants.

2. The' method deiined in claim 1 wherein a molar ratio-of alcohol to organic acid approxi- -mating but not substantially exceeding 2:1 is

used to form the reaction mixture.

JOHN HAROLD PERRINE.

JOHANNES H. BRUUN. 

